The present invention relates to novel pesticides and compositions containing them. The invention particularly pertains to compositions of said compounds and methods and use of said compounds for the control of arthropod, nematode, helminth or protozoan pests, in particular to the application of said compounds or compositions in agricultural methods of use, particularly as pesticides, for controlling arthropods, especially insects by systemic action.
The control of insects, nematodes or helminths by means of an active ingredient having a 1-arylpyrazole group therein has been described in such patent applications such as International Patent Publication No. WO 93/06089, WO 94/21606, WO 92/13451 and WO 87/03781 as well as in European Patent Publication Numbers 0295117, 659745, 679650, 201852 and 412849, German Patent No. DE19511269 and U.S. Pat. No. 5,232,940.
It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation.
A second object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole compounds against arthropods, especially insects, plant nematodes, or helminth or protozoan pests, particularly in agricultural or horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health.
A third object of the present invention is to provide very active compounds, with broad spectrum pesticidal activity, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, soil insecticidal and nematicidal, systemic, antifeeding or pesticidal activity via seed treatment.
A fourth object of the present invention is to provide compounds with substantially enhanced and more rapid activity, especially against insects and more particularly insects in their larval stages.
A fifth object of the present invention is to provide compounds with greatly improved (greater and faster) penetration into pest species when topically applied and thus provide enhanced movement of the compounds to the pesticidal site(s) of action within the pest.
Another object of the present invention is to provide compounds with high activity and improved safety to the user and the environment.
These and other objects of the invention shall become readily apparent from the detailed description of the present invention.
These objects are met in whole or in part by the instant invention.
The instant invention provides arylpyrazoles of formula (I): 
X is xe2x80x94Oxe2x80x94, or xe2x80x94NR17;
R1 is hydrogen, substituted or unsubstituted alkyl or a lone pair of electrons;
R2 is xe2x80x94S(O)nR18 or R19;
R3 is hydrogen, halogen, xe2x80x94C(O)R20, xe2x80x94S(O)pR21, alkyl, haloalkyl, xe2x80x94OR22, xe2x80x94Nxe2x95x90C(R23)(R24), alkenyl, xe2x80x94NR25R26, 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, or xe2x80x94CHxe2x95x90NOH;
R4, R5 and R7 are independently selected from hydrogen, halogen or alkyl;
R6 is halogen, haloalkyl, haloalkoxy, xe2x80x94S(O)qR27 or SF5;
R8 and R9 are independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, xe2x80x94OR28, xe2x80x94NR29R30 and xe2x80x94S(O)mR31, xe2x80x94C(O)R32, cyano or nitro; or
R8 and R9, together with carbon atoms to which they are attached may form a divalent alkylene radical which may be interrupted by one or more heteroatoms preferably selected from oxygen, nitrogen and sulfur;
R10, R11, R12 and R13 are independently selected from hydrogen, hydroxy, C(O)R32, alkyl and haloalkyl; or R10 and R11 can together form a carbonyl radical; or R12 and R13 can together form a carbonyl radical;
R14 and R15 are independently selected from R8; or R14 and R15 can together with the carbons to which they are attached a cyclic divalent alkylene radical which may be interrupted by one or more heteroatoms preferably selected from oxygen, nitrogen and sulfur;
R16 is alkoxy, alkyl or substituted or unsubstituted amino;
Y is oxygen or sulfur;
R17 is hydrogen, substituted or unsubstituted alkyl or a lone pair of electrons;
R18 is alkyl, alkenyl, alkynyl, or C3-C6 cycloalkyl, each of which is optionally substituted by one or more halogen;
R19 is alkyl or haloalkyl;
R20 is hydrogen, alkyl, haloalkyl, alkoxy or thioalkoxy;
R21 is alkyl haloalkyl, or aryl;
R22 and R23 are independently selected from hydrogen, alkyl and haloalkyl;
R24 is alkyl, haloalkyl, alkoxy or phenyl each of which is optionally substituted by one or more groups selected from hydroxy, halogen, alkoxy, xe2x80x94CN, alkyl, xe2x80x94S(O)r-alkyl;
R25 and R26 are independently selected from hydrogen, NH2, xe2x80x94S(O)rR34, xe2x80x94C(O)R35, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl and alkynyl; or R25 and R26 may form together a divalent alkylene radical which may be interrupted by one or more heteroatoms, preferably selected from oxygen, nitrogen and sulfur;
R27 is haloalkyl;
R28 is hydrogen, substituted or unsubstituted alkyl, xe2x80x94C(O)R33, or substituted or unsubstituted aryl;
R29 and R30 are independently selected from hydrogen, substituted or unsubstituted alkyl; or R29 and R30, may with the nitrogen to which they are attached form a divalent alkylene radical which may be interrupted by one or more heteroatoms;
R31 is alkyl haloalkyl or aryl;
R32 and R33 are independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, hydroxy, alkoxy, and substituted or unsubstituted amino;
R34 is substituted or unsubstituted alkyl;
R35 is hydrogen, alkyl, haloalkyl, aryl; alkenyl; xe2x80x94OR36, xe2x80x94SR37, or xe2x80x94NR38R39;
R36 and R37 are independently selected from hydrogen, alkyl haloalkyl and aryl;
R38 and R39 are independently selected from hydrogen, alkyl haloalkyl and aryl;
m, n, p, q, r, s, and t independently represent zero, one or two;
M is C-halo, Cxe2x80x94CH3, Cxe2x80x94CH2F, Cxe2x80x94CH2Cl, Cxe2x80x94NO2, or N;
or a pesticidally acceptable salt thereof;
provided that:
when A is (G4) and X is xe2x80x94Oxe2x80x94, R1 is a lone pair of electrons and the nitrogen to which R1 is attached forms a double bond with the central carbon of the G4 group;
when A is (G5), X is NR17 and R1 and R17 represent lone pairs of electrons;
when A is (G2), R10 and R11 are not simultaneously hydroxy:
when A is (G2), R12 and R13 are not simultaneously hydroxy.
By the term xe2x80x9cpesticidally acceptable saltsxe2x80x9d is meant salts the anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water soluble. Suitable acid addition salts formed from compounds of formula (I) containing an amine group, include salts with inorganic acids for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids for example acetates. Suitable salts with bases formed by compounds of formula (I) include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolamine or morpholine) salts.
Preferably by the term xe2x80x9csubstitutedxe2x80x9d is meant substituted by one or more of the following substituents: halogen, hydroxy, cyano, carboxyl, xe2x80x94C(O) alkyl, xe2x80x94C(O) O-alkyl, xe2x80x94C(O)NH2, xe2x80x94C(O)NH alkyl, xe2x80x94C(O)N (alkyl)2, aryl, nitro, azido, amino, alkylamino, dialkylamino, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, aryloxy, arylthio, alkylcarbonyl, amino, alkylcarbonyloxy, or aryloxycarbonyl.
Unless otherwise specified, alkyl groups and moieties including them have from one to six, preferably one to four, carbon atoms, alkenyl groups have from two to six, preferably two to four, carbon atoms, and alkynyl groups have from three to six, preferably three to four carbon atoms. By the term xe2x80x9carylxe2x80x9d is meant mono or polycyclic aromatic moieties, preferably including phenyl, pyridyl, pyrimidinyl, furyl and naphthyl groups. The term xe2x80x9chaloxe2x80x9d before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br or 1, in any combination, preferably F or Cl. The term xe2x80x9chalogenxe2x80x9d means F, Cl, Br or I. It shall be understood that the rings formed by the divalent alkylene radicals which includes the atoms to which they are attached are generally 5, 6 and 7 membered rings.
A preferred class of a compound of formula (I) are those with one or more of the following features:
A is (G1), (G3) or (G4);
R1 is hydrogen or a lone pair of electrons;
R8 and R9 are selected from alkyl, haloalkyl and hydrogen; or Y is oxygen.
A very preferred class of compounds of formula (I) is that wherein:
A is (G3);
Y is oxygen or sulfur;
R1 is hydrogen or alkyl;
R2 is xe2x80x94S(O)nR18;
R3 is NR25R26;
R4 is halogen;
R5 and R7 are hydrogen;
R6 is haloalkyl;
R18 is alkyl;
R25 and R25 are independently selected from hydrogen or alkyl.
Another very preferred class of compounds of formula (I) is that wherein:
A is (G1);
R8 and R9 are independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl and xe2x80x94C(O)R32;
R1 is hydrogen;
R2 is xe2x80x94S(O)nR18;
R3 is xe2x80x94NR25R26;
R4 is halogen;
R5 and R7 are hydrogen;
R6 is haloalkyl;
R18 is alkyl;
R25 and R26 are independently selected from hydrogen or alkyl; and
R32 is alkyl, haloalkyl, alkoxy, or hydroxy.
Another very preferred class of compounds according to the instant invention is that wherein:
A is (G4);
R8 is alkyl or haloalkyl, preferably methyl or halomethyl;
X is xe2x80x94NHxe2x80x94or O;
R1 is a lone pair of electrons;
R2 is xe2x80x94S(O)nR18;
R3 is xe2x80x94NR25R26;
R4 is halogen;
R5 and R7 are hydrogen;
R6 is haloalkyl;
R18 is alkyl; and
R25 and R26 are independently selected from hydrogen and alkyl.
Another very preferred class of compounds of formula (I) is that wherein:
A is (G2);
R1 is H or alkyl;
X is xe2x80x94Oxe2x80x94or xe2x80x94NHxe2x80x94;
R10, R11, R12 and R13 are selected from hydrogen, xe2x80x94OH, and xe2x80x94C(O)R32;
R2 is xe2x80x94S(O)nR18;
R3 is xe2x80x94NR25R26;
R4 is halogen;
R5 and R7 are hydrogen;
R6 is haloalkyl;
R18 is alkyl;
25 and R26 are independently selected from hydrogen and alkyl; and
R32 is alkoxy or amino.
Preferred aryl groups comprising the R4 to R7 and M radicals in formula (I) are: 2,6-dichloro-4-trifluoromethylphenyl; 2,6-dichloro-4-trifluoromethoxyphenyl; 2-bromo-6-chloro-4-trifluoromethylphenyl; 2-bromo-6-chloro-4-trifluoromethoxyphenyl; 2,6-difluoro-4-trifluoromethylphenyl; 2-chloro-4-trifluoromethylphenyl; 3-chloro-5-trifluoromethyl-2-pyridinyl; 3-chloro-5-trifluoromethoxy-2-pyridinyl; 2-bromo-6-fluoro-4-difluoromethylphenyl; 2-chloro-6-fluoro-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethylphenyl; 2,6-dibromo-4-trifluoromethoxyphenyl; and 2,6-dichloro-4-pentafluorothiophenyl.
Among the compounds of general formula (I) are the following particularly preferred compounds which provide particularly useful control of insect species by systemic action. The compound numbers are for reference only.
Wherein R3 is NH2; R4 is CI, M is Cxe2x80x94Cl, R5xe2x95x90R6=H; R6 is CF3 and
1) A is G4, X is O, R2 is SOCH3, R8 is CF3: m.p. about 159xc2x0 C.;
2) A is G4, X is O, R2 is SOCH3, R8 is CCl3: m.p. about 98xc2x0 C.;
3) A is G4, X is O, R2 is SOEt, R8 is CF3: m.p. about 155xc2x0 C.;
4) A is G4, X is O, R2 is SOCH3, R8 is CF3: m.p. about 156xc2x0 C.;
5) A is G4, X is O, R2 is SCH3, R8 is CH3: m.p. about 75xc2x0 C.;
6) A is G4, X is NH, R2 is SOCF3, R8 is CF3: m.p. about 81xc2x0 C.;
7) A is G1, X is NH, R2 is SOCH3, R9 is H, R8 is xe2x80x94C(CH3)2CH2OH: m.p. about 207xc2x0 C.;
8) A is G1, X is NH, R2 is SOCH3, R9 is H, R8 is CF3: m.p. about 109xc2x0 C.;
9) A is G1, X is NH, R2 is SOCH3, R9 is H, R8 is 2-furanyl: m.p. about 120xc2x0 C.;
10) A is G1, X is NH, R2 is SOCH3, R9 is H, R8 is (3-methyl)phenyl: m.p. about 120xc2x0 C.;
11) A is G1, X is NH, R2 is SOCH3, R9 is H, R8 is xe2x80x94COOH: (oil);
12) A is G1, X is NH, R2 is SOCH3, R9 is H, R8 is phenyl: (oil);
13) A is G1, X is xe2x80x94Oxe2x80x94, R2 is SOCH3, R9 is H, R8 is CH3: m.p. about 204xc2x0 C.;
14) A is G1, X is xe2x80x94Oxe2x80x94, R2 is SOCH3, R9 is H, R8 is phenyl: m.p. about 118xc2x0 C.;
15) A is G7, X is O, R2 is SOCH3, R9 is H, R8 is ethyl: m.p. about 11 1xc2x0 C.;
16) A is G3, Y is O, X is NH, R1 is H, R2 is SOCH3: m.p. about 207xc2x0 C.;
17) A is G3, Y is O, X is NH, R1 is isopropyl, R2 is SOCH3: (oil);
18) A is G3, Y is S, X is NH, R1 is H, R2 is SOCH3, (oil);
19) A is G2, X is O, R1 is H, R2 is SOCH3, R10 is methyl, R11 and R12 are hydroxy, R13 is H: m.p. about 194xc2x0 C.;
20) A is G2, X is O, R1 is H, R2 is SOCH3, R10 is H, R11 and R12 are hydroxy, R13 is H: m.p. 207xc2x0 C.;
21) A is G8, X is NH, R1 is H, R2 is SOCH3, R10 is H, R11 and R12 are xe2x80x94COOEt, R13 is H: m.p. about 95xc2x0 C.;
22) A is G8, X is NH, R1 is H, R2 is SOCH3, R10 is H, R11 and R12 are xe2x80x94CONH2, R13 is H; and
23) A is G5, X is NR17, R1 and R17 are lone pairs of electrons, R14 and R15 are H, R2 is SOCH3: m.p. about 160xc2x0 C.
According to a further feature of the invention, compounds of general formula (I) are prepared from compounds of formula (II): 
by reaction with:
a) in the case of A=G1, an aldehyde or ketone of-general formula R8C(O)R9 generally in the presence of an acid such as hydrogen chloride and optionally in the presence of a water removal means, the reaction being generally effected in a solvent such as methylene chloride and at the reflux temperature of the solvent;
b) in the case of A=G2, an aldehyde or ketone of general formula R10C(O)C(O), R13 wherein R10 and R13 are independently selected from hydrogen or alkyl, generally in the presence of an acid such as hydrogen chloride and optionally in the presence of a water removal means, the reaction being generally effected in a solvent such as methylene chloride and at the reflux temperature of the solvent or with a compound of general formula R10R11CLCLR12R13; wherein xe2x80x98L and Lxe2x80x99 are leaving groups such as halogen; and wherein R10R11R12 and R13 are not hydroxy, generally in the presence of a base and optionally in a solvent; or with a compound R32C(O)CC(O)R32 in the optionally in the presence of a base;
c) in the case of A=G3, phosgene or thiophosgene, carbonyldiimidazole, or other phosgene equivalents known to persons skilled in the art of chemical synthesis, generally in the presence of a base such as pyridine or an alkali metal carbonate in a solvent such as methylene chloride and at a temperature generally fromxe2x80x94100xc2x0 to 100xc2x0 C.;
d) in the case of A=G4, and R1 is H, an orthoester, in the presence of an acid catalyst such as para-toluene sulfonic acid, the reaction generally being effected in a solvent which can be an alcohol (such as ethanol) and generally at the reflux temperature of the solvent;
e) in the case of A=G5, wherein X is NH and R17 is H, a dicarbonyl compound of formula R14C(O)C(O)R15 in the presence of an acid catalyst such as hydrogen chloride optional water removal means and optionally in a solvent, the temperature of the reaction generally being at the reflux temperature of the solvent;
f) in the cases of A=G6 and G7 with phosphorylating sulfenylating, sulfinylating or sulfonylating reagents such as ethyldichlorophosphate, ethyldichlorothiophosphate, thionylchloride, sulfonyl chloride, sulfur monochloride and the like; and generally in the presence of a base such as methylamine or sodium hydrogen carbonate and optionally in the presence of a solvent.
According to a further feature of the present invention compounds of general formula (II) in which R1 is H may be prepared by the reaction of a compound of formula (III): 
with a compound of formula (IV)
H2NXxe2x80x94Hxe2x80x83xe2x80x83(IV)
in which X is defined above. The reaction is generally performed using an acid salt of a compound of formula (IV), for example the hydrochloride salt, and in the presence of a base for example pyridine or an alkali metal carbonate (such as sodium carbonate) or an alkali metal acetate (such as sodium acetate) or ammonium acetate in a solvent such as methanol and/or water at a temperature from 0xc2x0 C. to 100xc2x0 C.
According to a further feature of the present invention compounds of general formula (II) wherein R1 is H may be prepared by the reaction of a compound of formula (V): 
wherein R represents alkyl, with a compound of formula (IV). The reaction is generally performed using an acid salt of a compound of formula (IV), for example the hydrochloride salt, and optionally in the presence of a base (for example pyridine or an alkali metal carbonate such as sodium carbonate) or an alkali metal acetate (such as sodium acetate or ammonium acetate) in a solvent such as methanol and/or water and generally at a temperature from 0xc2x0 C. to 100xc2x0 C.
According to a further feature of the invention, compounds of formula (II) wherein R1 is alkyl may be prepared from compounds of formula (II) wherein R1 is H by alkylation, a process known to those skilled in the art of chemical synthesis.
The compounds of formula (III) wherein R2, R3, R4, R5, R6 and M are the above described substituents can be prepared by methods described in one or more of the following: WO 94/21606, WO 93/06089, WO 87/03781, WO 97/22593; European Patent Publications EP 0295117, EP 0511845, EP 0403309, EP 0403300, EP 352944, EP 780378; U.S. Pat. Nos. 5,232,940, 5,047,550, 4,918,085; German Patent Publication No. 19511269; or by methods known to those skilled in the art.
The synthesis of high oxidation states of the compounds of formula (I), i.e., compounds in which m, n, p, q, r, and s are 1 or 2, can be achieved by oxidation of the corresponding compounds in which those variables are 0 or 1.
Intermediates of formula (III) may be prepared by known methods (see for example the above listed references).
Certain compounds of formula (III) are novel and as such constitute a further feature of the invention.